Stilbene dicarboxylic acid amides



2,898,371 Patented Aug. 4, 1959 STILBENE DICARBOXYLIC -ACID AMIDES sulfonic :groups;

. 2 V In carrying out the synthesis of the dyes of the present invention, an exceedingly wide range of compounds may be used, resulting in the production of numerous attractive shades in the finished product.

Robert S. Long, Bound Brook, and Sien Moo Tsang,

Middlesex, N .J., assignors to American .Cyanamid Company, New York, N.Y., a corporation of Mame No Drawing. ApplicationDecember 16, 1957 Serial No. 702,798

6 Claims. (Cl. 260-507) This invention relates to intermediates for new dyes and, more specifically, it relates to new dye intermediates; 3

of the structure:

in which Z and Z are carbocyclic aryl radicals of less than three six membered rings which are further substituted by at least one group selected from hydroxy, amino, acetoacetamino and l-pyrazolyl. These compounds are coupling components from which new azo dyes canbe prepared.

When azo dyes which contain a free amino group are condensed with the acid chloride of stilbene dicarboxylic acid, there are formed new azo dyes which have excellent substantivity for cellulosic fibers. It is affurther advantage that these new dyes in general'have excellent fastness to light and washing, often superior to available commercial types. These new azo dyes may be represented by the formula i For example, synthesis by Route 2 can utilize such 'nitroamines as -5 -nitro-2-aminotoluene, 4-nitroaniline-2- sulfonic acid, 5-nitro-2-aminoaniso1tb 2-nitro-4-methyl- S-arninoanisole, 3-nitro-4-chloro-aniline, 4-nitro-2-aminotoluene, I 4-nitro-2-aminoanisole, 6-nitro-4-amino-l,3-d1- methylbenzene, 3-nitro-l-naphthylamine, '4-nitro-1-naphthylamine, S-nitro-l-naphthylamine, 1-chlor-2-arnino-4- nitronaphthalene; These can be coupled into the various' naphtholsulfonic acids known to the art, into naphthols such as beta -naphthol, and into phenols, such as salicylic acid, phenol; cresols, resorcinol, and the like.

They may also be coupled into naphthylamines such as 2-naphthylamine-5,7-disulfonic acid, gamma acid, or J acid in such a way that coupling is ortho to the amino group. By using Route 1, one can couple various diazo compounds such asthose from aniline, toluidines, anisidinesfarrlinosalicylic acids, and aminonaphthalene compounds such as H acid, amino G acid, K acid, Cassellas acid, gamma'acid, and the like with aniline and naphthylannne derivatives.

' It is a further advantage of these new azo dyes that when the starting materials are chosen so that metalliz able groups (e.g., hydroxy, alkoxy, halogen, carboxy) are present ortho to the azo linkage in the aminoazo 'intermediate, it is-possible, after condensation withpstilbene dicarbonylchloride, to metallize the final dyestuifs to obtain very valuable dyes with excellent fastness properties.

Azo dyes of this general type may also be prepared by a third route. If the stilbene dicarboxylic acid is condensed with an aminophenol, an aminonaphthol, or

in which R and Ar are aromatic residues of notmore than tworings. i

The amino azo dyes which are to be reacted with stilbene dicarboxylic acid are prepared in several ways.

diarnino' benzene or naphthalene, the resultant amide can be used as a coup-ling component for 'diazotized amines and the products are also azo dyes of the type contemplated.

pound thus prepared is reacted with stilbene dicarbonyl chloride to form the dyes of this invention. These new azo dyes are claimed in our copending application, Serial No. 401,376, filed December 30, 1953, of which this application is a continuation in part.

Both of the carbocyclic aromatic residues which form the aminoazo compound can be either naphthalene or benzene derivatives. They can be further substituted by alkyl, alkoxy, hydroxy, halogen, amino, carboxy, or v -Thesefcoupling components are alsonew compounds and thelspecific embodiment of the present invention. They are derived from such aminophenols, aminonaphthols, and diamino compounds as m-aminophenol, m-phenylcne diamine, m-toluylene diamine, S-amino-Z-naphthol,

8-amino-2-naphthol, J acid, gamma acid, H acid, Chicago acid; aminoacetoacetanilides, and aminophenylpyrazolones. These compounds all have in common not only the amino group to be acylated, but also a group which activates coupling of diazonium compounds such as amino or hydroxyl. .This route to the azo dyes of our invention has an advantage over the other routes in that one starting material. The products prepared by this route show excellent fastness to chlorine. a Q

i The stilbene dicarboxylic acid amides can be prepared by a variety of conventional methods. This, the stilbene dicarboxylic acid may be converted to the di-acid chloride by the use of phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride, thionyl chloride, or a similar agent. The acid chloride may then be reacted with two moles of the amine or aminoanumber' of different dyes can be readily preparedfr om 1 specified.

parts of water.

i for twenty-four hours.

3 azo compound, in thepresence of an inert solvent if necessary. A convenient method is to'heat the dicarboxylic acid in an excess of thionyl chloride under reflux, to distill 01f the excess reagent, and to treat the acid chlo- -'ride"with the amine in pyridine-at the boil. Stillbetter,

the dicarboxylic acid is reacted with only the theoreti- -cal amount of thionyl chloride by gentle=warming in -pyridine, and the amine is then added directly to the -reaction mixture, which is then heated at the' boiling "point. An alternative method whereby one may'is'olate the-acid chloride in pure form is to heat the dicarboxylic acid'with-the theoretical amount of thionyl chloride in "anindifferent medium such as nitrobenzene; the acid "chloride precipitates out andmay be filtered ofi; -it is then reacted with the amine as before.

Our invention can be illustrated by the following examples, inwhich parts are by weight unless otherwise Example 1 NH-C 00-01}: 2

Sti1bene-4,4'-dicarboxylic acid chloride is prepared by refluxing a mixture of 1.34 parts of stilbene-4,4-dicarboxylic acid with 16.4 parts of thionyl chloride. After being stripped of excess thionyl chloride, the acid chlopurified twice by recrystallization from the aqueous so- OONa -If 2-aminophenol-4-sulfonic acid is substituted in equivalent amount for the J acid, the corresponding dilution.

' amide is obtained.

Example 2 SO NA NaO S The diamide from Example 1, 1.43 parts, is dissolved in a solution of 1.2 parts of sodium carbonate in Example 3 A mixture of 10.72 parts of stilbene-4,4'-dicarboxylic acid, 13.83 parts of thionyl chloride and 393 parts of dried pyridine is heated at 55 C. until the reaction is complete. Twenty-five partsof gamma acid is then add ed. The resulting mixture is heated at reflux until the reaction is' substantially complete. It is drowned into 500 parts of water containing 100 parts of sodium chloride and 12 part sof sodium carbonate. After the removal of the pyridine by steam distillation, the mixture is clarified by filtration. When the mixture is cooled, the diamide separates. It is filtered, washed with 10% sodium chloride solution and dried.

Example 4 NHCO-CH= iThe dye is obtained by coupling 2.76 parts of the diamide with a slight excess anthranilic acid diazo at 10-15 C. in 80 parts of water containing 3.3 parts of .sodium carbonate as the neutralizing agent. The dye is separated by salting with 10 parts of sodium chloride and'isolated by filtration. It dyes cotton a scarlet shade which turns bluer on after-treatment with copper or chromium salt.

0 0 ONE Example 5 Benzidine tetrazo is prepared from 2.57 parts of benzidine dihydrochloride by the usual method of tetrazotizaas described in Example 5) in 150 parts of water and 19.6 parts of pyridine is added, with 1.06 parts of sodium carbonate present as the neutralizing agent. The reaction is efiected at 10 C. The dye is separated by -.salting.and filtering. 1 It dyes cotton a reddish brown 10 shade with good wash and light fastness.

Example 6 The resulting solution is cooled to 10 C. and treated with a slight excess of the diazo from 3-amino-4-methoxybenzene sulfonic acid which is obtained bythe usual methodof diazotization. The bisazo dye is separated by filtration. It dyes cotton a reddish orange shade. V

The dye is metallized by heating with a mixture of A mixture of 1 part of 4,4-stilbene dicarboxylic acid, 720 parts of dry pyridine, and 0.89 part of thionyl chloride was heated with stirring at 505S C. until formationof the acid chloride was complete. The mixture 'was then refluxed with 1.31 partsof l-arnino-7-naphthol until" the condensation was complete. A grey solid was precipitated by pouring the dark brown solution into 200 parts of water, and it was filtered oif. The solid was ftak'en up in parts of ethanol and 7.6 parts of 5 N potassium hydroxide, and the solution was heated on -'thesteam bath-while gradually adding parts of water. "A'sm'allamount of sediment was filtered off and a curdy a w t.

Example 7 The product of Example 6 was coupled on cotton cloth 'with a number of stabilized diazonium compounds of the type known as fast bases. The following colors were obtained:

Fast base from: Color l-aminoanthraquinone Pink. S-nitro-p-anisidine Bordeaux. S-nitro-o-anisidine Blue red. Dianisidine Blue.

Example 8 The procedure of Example 6 is used substituting 0.9 part of m-aminophenol for the 1-amino-7-naphthol. A good yield of sti1bene-4,4'-dicarboxy-m-hydroxyanilide is obtained. This may be used to couple with fast bases in a manner similar to that used in Example 8.

Example 9 [9mm oOon=l The procedure of Example 6 is followed using m-aminoacetanilide. The crude acetamido product, when heated with the caustic in ethanol is hydrolyzed to the free amine which precipitates and is purified by recrystallization from aqueous ethanol.

6 We claim: 1. Compounds having the structure:

in which Z is a carbocyclic aryl radical of less than 3 six membered rings further substituted by at least one group selected from hydroxy, amino, acetoacetamido, and pyrazonyl.

2. Compounds according to claim 1 in which Z is a naphthalene residue.

3. Compounds according to claim 2 in which Z is sulfonated.

4. A compound having the formula:

-NHC 00-011:

OH 2 5. A compound having the formula:

NHO 00011:]

.L 6. A compound having the formula:

References Cited in the file of this patent UNITED STATES PATENTS HOZS 2,521,665 Hausermann Sept. 5, 1950 2,567,796 Aekermann Sept. 11, 1951 2,688,617 Hein et a1 Sept. 7, 1954 

1. COMPOUNDS HAVING THE STRUCTURE: 